Recently, the large number of investigations concerning acid-catalyzed photopolymer systems such as chemically amplified photoresists and UV-curing materials has been reported. On the other hand, analogous systems utilizing base-catalyzed reactions have received far less attention, because low quantum yields for photobase generation to lead to low photosensitivity of these systems. To improve this problem, we proposed introduction of the concept of base proliferation reactions into the photopolymer systems using base-catalyzed reactions. The concept involves the autocatalytic base-catalyzed decomposition of a compound, referred to as a base amplifier which releases a newborn amine, leading to its autocatalytic decomposition. In fact, the addition of the base amplifiers such as 9-fluorenylmethyl carbamate, phenylsulfonylethyl carbamate, and 3-nitropentane-2-yl carbamate to a photopolymer consisting of an epoxy polymer sensitized and a photobase generator (PBG) resulted in the marked improvement of photosensitivity.
However, these base amplifiers with low molecular weight are not suitable for photopatterning because of the volatility and the excessive diffusion of amines proliferated in polymer films. We report here novel base-amplifying silicone resins tethering phenylsulfonylethyl carbamoyl groups which proliferate primary amino groups or secondary amino groups in their side chains.
Base-catalyzed decomposition behavior of films of these resins containing PBG was evaluated by UV absorption measurements. A film consisting of the resin proliferating primary amino groups and 10 wt% of PBG decomposed immediately in a nonlinear manner by 365 nm irradiation and subsequent heat treatment at 120oC for 6 min. On the other hand, this film without UV irradiation was thermally stable for 18 min at 120oC. These results indicate that photoinduced base proliferation reaction of the resin proceeded. A film consisting of the resin generating secondary amino groups and PBG decomposed in a way similar to that of the resin proliferating primary amino groups. Furthermore, lithographic evaluation of the film comprising the resin to generate secondary amines and PBG obtained 7ÊS positive images with an exposure dose of 75 mJ/cm2 which shows higher sensitivity when compared to conventional base-catalyzed photopolymers.